KR100766370B1 - Transparent substrate provided with a stack of thin layers acting on solar radiation and monolithic glazing or double glazing incorporating said substrate - Google Patents

Abstract

A coated transparent substrate has a metallic or nitrided niobium, tantalum and/or zirconium functional layer and an aluminum and/or silicon nitride and/or oxynitride cover layer. A transparent substrate has a solar radiation active thin film stack comprising a functional layer based on metallic or partially or fully nitrided niobium, tantalum and/or zirconium covered by a layer based on aluminum nitride, aluminum oxynitride, silicon nitride and/or silicon oxynitride. Independent claims are also included for the following: (i) single or double glazing incorporating the above substrate; and (ii) a curtain wall-type facade face panel incorporating the above substrate with an opaque coating. Preferred Features: The substrate consists of clear or tinted glass or a flexible or rigid transparent polymer.

Description

TRANSPARENT SUBSTRATE PROVIDED WITH A STACK OF THIN LAYERS ACTING ON SOLAR RADIATION AND MONOLITHIC GLAZING OR DOUBLE GLAZING INCORPORATING SAID SUBSTRATE}

The present invention relates to glazings with stacks of thin layers acting on solar radiation, in particular glazings used for thermal insulation and / or sun protection.

This type of glazing is more particularly suitable for installation in buildings. This thin layer can help to limit the amount of solar radiation needed to limit the energy consumption needed to condition the room by preventing excessive heating of the interior of the room in summer.

The invention also relates to this type of glazing once opaque to form part of a wall cladding panel, more precisely referred to as "curtain walling", which is combined with window glazing in its entirety. To provide the building with a glazed exterior surface.

There are a number of limitations to this multilayer glazing (and curtain walling). With regard to window glazing, the layers used must sufficiently filter out solar radiation. In addition, thermal performance must preserve the optical and aesthetic appearance of the glazing. It is desirable to be able to control the level of light transmission of the substrate and, in particular, to maintain aesthetically noticeable color upon external reflection. This also applies to curtain walls with respect to their appearance upon reflection. This layer must also be sufficiently durable, which, once fitted in glazing, must be more durable if the layer is on one of the outer surfaces of the glazing (eg, in the middle of a double-glazing unit). Opposite the "inner" side towards the intermediate gas-filled cavity}.

Other constraints are imposed gradually. If the glazing consists at least in part of a glass sheet, such a glass sheet may, for example, be molded into a glass sheet {the shopwindow of the shop} bending, or to make the glass sheet stronger / less dangerous during impact. It may be desirable to undergo one or more heat treatments, such as toughening or annealing operations. The fact that the layer is deposited on the glass before the heat treatment means that the layer is damaged and there is a risk of substantially altering the properties of the layer, in particular the optical properties (it is difficult and expensive to deposit the layer after the glass has been heat treated).

The first approach is to change the optical appearance of the glass by the layer after heat treatment and to configure the layer so that only after the heat treatment the layers have the desired properties, in particular optical and thermal properties. But in fact this means that one must manufacture two types of multi-layer stacks in parallel, one for non toughening / non-bending glazing and the other for toughening / bending glazing. Subsequently, attempts are avoided by devising a stack of thin (interfering) layers that can withstand heat treatment without significantly altering the optical properties of the glass and without deteriorating the appearance (optical defects). The layer can therefore be called "bendable" or "toughenable".

Examples of sun shield glazing for buildings are given in patents EP-0 511 901 and EP-0 678 483. It is made of nickel-chromium alloy selectively nitrided to filter out solar radiation, made of stainless steel or tantalum, and made of two dielectric layers of metal oxides such as SnO ₂ , TiO ₂ and Ta ₂ O _5. Refers to a functional layer located between Such glazing results in excellent sun protection glazing with satisfactory mechanical and chemical durability, but the oxidation of the functional layer during the bending or toughening operation of the oxide layer surrounding the functional layer (oxidation alters the light transmittance and the general appearance of the glazing It is not truly "bendable" or "strengthenable" because it does not prevent it from being completely altered).

Many studies have recently been carried out to make the layers bendable / tough with regard to low-emissivity glazing, the aim of which is to achieve high light transmittance rather than sun protection. It has already been proposed to use a silicon nitride based dielectric layer over a silver functional layer, since the silicon nitride material is relatively inactive against high temperature oxidation, as described in patent EP-0 718 250. Proved to be appropriate for protecting the layer.                 

Another multilayer stack has been described which acts on solar radiation and is assumed to be bendable / toughable, which uses a functional layer rather than silver. Patent EP-0 536 607 uses a functional layer made of TiN or CrN type metal nitride with a protective layer made of metal nitride or a silicon derivative. Patent EP-0 747 329 describes a functional layer of a NiCr type nickel alloy combined with a silicon nitride layer.

However, the performance of these stacks providing sun protection is still possible, particularly in terms of durability and resistance to deterioration in quality when passing through high temperature heat treatments.

The term " functional " layer is generally made of a dielectric material in the present invention and, in contrast to other layers having a function of chemically or mechanically protecting the functional layer, such as optical function, adhesive layer function, etc. Note is understood to mean a layer in a stack.

It is therefore an object of the present invention to develop a new type of thin stack that acts on solar radiation in order to produce improved sun protection glazing. The intended improvement is to obtain a better compromise between durability, thermal properties, optical properties and the ability to withstand heat treatment without any damage, especially if the plate carrying the stack is of the glass type.

Another object of the present invention is to make this multilayer stack well suited to the use of glazing once the glazing becomes opaque like curtain walling.

Summary of the Invention The gist of the present invention is, above all, a transparent sheet made of glass, with a thin stack, which acts on solar radiation, which stack comprises essentially at least one functional layer of metallic properties, niobium, tantalum and zirconium Mainly comprising at least one of the metals belonging to the group consisting of: the functional layer is based on silicon nitride or oxynitride or based on aluminum nitride or oxynitride or a mixture of at least two of these compounds (Si-Al mixed Nitride or oxynitride).

Alternatively, the functional layer according to the invention may be based on a partially or wholly nitrided metal, which belongs to the group consisting of niobium, tantalum and zirconium.

The combination of this type of functional layer with this type of coating layer proves to be very advantageous for sun protection glazing. That is, functional layers of type Nb, Ta or Zr are particularly stable and are more suitable than other functional layers already used for the same type of application to withstand several heat treatments, regardless of the nature of the coating layer. For example, niobium tends to be less oxidized than other metals such as titanium and nickel, and it has virtually proved that the selected metals are also more stable than Ni-Cr alloys containing large amounts of chromium, which is due to the effects of heat. This is because there is a tendency to diffuse into the adjacent layer and the adjacent glass, and thus a tendency to completely optically change the multilayer stack.

Moreover, while the functional layer of the present invention makes it possible to change the light transmittance value of the sheet by adjusting the thickness of the functional layer within the desired range described below, even with a relatively high light transmittance, it has a significant sun protection effect. Keep it up. In other words, the functional layer is in a fully selective, in particular, light transmission (T _L) level and the solar factor (solar factor) (SF) (solar factor is defined as the ratio of the total energy entering the room through the glazing to the incident solar energy To achieve a good compromise. "Excellent" trade-off is when the T _L and the SF value of a sun block glazing be similar to each other, for example, SF up to 5-10% less than T _L, specifically, it can be at times defined higher up to 2 to 3% than T _L have. This trade-off is there may be represented by comparing the T _L value and the energy transmittance value T _E, "excellent" compromise when similar to the value T _E a T _L value, for example within about 5% of the T _L value, in detail Is obtained when it is about 2 to 3%. Based on silicon nitride or aluminum nitride (which are outlined as Si ₃ N ₄ and AlN) or silicon oxynitride or aluminum oxynitride (which is outlined as SiON and AlNO without considering the respective amounts of Si, O and N) Choosing a coating layer based on has proven to be very advantageous for several issues as well. That is, when the plate comprising the stack is made of glass and when the stack is required to be heat treated after depositing the layer, this type of material can protect the functional layer of the invention against high temperatures, in particular against oxidation. On the other hand, since it is proved that the functional layer can be maintained completely, the stack can be made bendable / toughable by the present invention. In other words, both the light transmittance and the appearance at the time of reflection change so little that they cannot be sufficiently perceived by the naked eye, so the change in the optical properties generated by the toughening type heat treatment is negligible.

Moreover, the refractive index of the coating layer based on silicon nitride or aluminum nitride or based on silicon oxynitride or aluminum oxynitride is approximately 2, which is similar to the refractive index of SnO ₂ or ZnO type metal oxide. That is, optically, similar to SnO ₂ or ZnO without any particular complexity. It also provides accurate mechanical and chemical protection for the rest of the stack.

Finally, it has been found that the coating layer is also well suited for subsequent enameling. In general, a possible method of opaque glazing for curtain walling is to deposit a lacquer on glass, to cure and dry with appropriate heat treatment, and Since there are two ways of depositing enamel, this is particularly advantageous in the case of curtain walling. As is commonly deposited, enamel is also called powders and vehicles containing glass frits (glassy matrix) and pigments used as colorants (frits and pigments based on metal oxides). And a medium that is applied to the glass and adheres to the glass upon deposition. In order to obtain the final enameled coating, the enamel must be baked, and this baking is often carried out simultaneously with the toughening / bending of the glass. For further details regarding the enamel composition, reference may be made to patents FR-2 736 348, WO 96/41773, EP-718 248, EP-712 813 and EP-636 588. Enamel, a mineral coating, is a useful opaque coating because it is durable and sticks to glass. However, if thin layers were previously provided for glazing, using them is tricky for two reasons:

On the other hand, of course, baking an enamel means a high temperature heat treatment of the multilayer stack, which is only possible if the stack cannot be optically degraded during the heat treatment.

On the other hand, over time, enamel tends to release chemicals, which diffuse into the adjacent layer and chemically change the adjacent layer.

However, the use of a layer of silicon nitride or silicon oxynitride or aluminum nitride or aluminum oxynitride to complete the thin stack is such a chemical compound that can withstand the heat treatment and can diffuse out of the enamel layer. It was very effective at acting as a barrier to. As a result, the multilayer stack according to the invention can be enameled in that enamel can be deposited and baked on the stack without noticeably altering the optical appearance for window glazing provided with the same layer upon external reflection. have. It is really worthwhile for curtain walling to provide color harmonization and to make the exterior as similar as possible with window glazing in order to be able to create aesthetically noticeable and totally glazed walls.

Combining the functional layer and the coating layer by the present invention also has other advantages. That is, although Si ₃ N ₄ , SiON, AlN and AlNO have the very useful properties mentioned above, they also tend to cause problems of adhesion to many metal layers. This is especially the case for silver layers. Therefore, it is necessary to use a method that increases this adhesion and prevents the stack from delaminating. That is, in particular, an adhesive layer can be inserted, for example a thin layer of metal or layer based on zinc oxide, which shows good compatibility between the two materials in question. The presence of this adhesive layer is unnecessary in the environment of the present invention. Thus, the functional layer of the present invention, in particular the Nb layer, is very suitable for Si ₃ N ₄ , SiON, AlN and AlNO layers using sputtering deposition techniques, in particular magnetic-field-enhanced sputtering. It has been confirmed that it adheres satisfactorily.

Optionally, the multilayer stack according to the invention comprises at least one sublayer made of a transparent dielectric material, ie silicon nitride or silicon oxynitride and / or aluminum nitride or aluminum oxynitride, as in the coating layer, between the plate and the functional layer, Or even one selected from silicon oxide (SiO ₂ ).

This sublayer allows for a more flexible change in the optical appearance given by the multilayer stack on the carrier plate of the sublayer. Moreover, in the case of heat treatment, the accessory layer forms additional barriers, in particular against alkali metals and oxygen in the glass sheet, which alkali metals and oxygen are likely to diffuse by heat and cause degradation of the stack quality.

A preferred embodiment is to use a coating layer and sublayers made of nitride or oxynitride, both of which are based in particular on silicon nitride.                 

In this case one embodiment has proven to be advantageous to make a coating layer which is for example at least 1.2 or 1.5 or 1.8 times thicker than the accessory layer. The coating layer may even be 2, 3 or 4 times thicker (this thickness refers to the geometric thickness), since it has been described in the present invention that the thicker the coating layer, the better the optical stability with respect to the toughening type of heat treatment is ensured. to be.

By other embodiments that do not exclude the previous example, in particular, it may be provided to use a multilayer sublayer in which a high refractive index (eg 1.8 to 2.2) and a low refractive index (eg 1.4 to 1.6) are alternated. have. This is preferably an arrangement of Si ₃ N ₄ (refractive index about 2) / SiO ₂ (refractive index about 1.45) or Si ₃ N ₄ / SiO ₂ / Si ₃ N ₄ types. This arrangement allows the appearance of the plate during reflection to be adjusted in particular to reduce the R _L value and / or the color of the plate.

The multilayer stack according to the invention may optionally comprise further layers of nitride of at least one metal selected from niobium, titanium, zirconium and chromium above and / or below the functional layer. This layer can therefore be actually inserted between the functional layer and the covering layer and / or between the functional layer and the plate (or between the functional layer and the sublayer if there is only one). Therefore, if the functional layer itself is a nitride, two nitride layers based on different metals may overlap.

By reducing the thickness of the functional layer to the extent that this additional nitride layer allows, it has been demonstrated that the color of the stack can be finely adjusted upon external reflection. Therefore, it is possible to "replace" a portion of the functional layer thickness with this additional layer.                 

Advantageously, the layer or layers of the stack based on silicon nitride or silicon oxynitride also comprise a small amount of metal compared to silicon, for example up to 10% by weight of the compound constituting this layer, in particular aluminum. . This is useful for increasing the deposition rate of a layer by magnetic-field-enhanced and reactive sputtering, where a silicon target is sufficient if it does not "doping" with any metal in this sputtering. It is not conductive. Moreover, metals can provide better durability against nitrides or oxynitrides.

Regarding the thickness of the layer described above, it is usual to select a thickness in the range of 5 to 50 nm, in particular in the range of 8 to 40 nm, for the functional layer. By selecting the thickness of the functional layer, the light transmittance of the sheet can be varied within the range used for glazing to provide sun protection to the building, ie within the range of 5% to 50% or 8% to 45%. Of course, the light transmittance level can also be changed using other parameters, in particular the thickness and composition of the plate, especially when the plate is made of transparent glass or colored glass.

It is preferable that the thickness of a coating layer is 5-70 nm, specifically 10-35 nm. For example, the thickness of the coating layer is 15, 20 or 30 nm.

The thickness of the optional sublayer is preferably from 5 to 120 nm, in particular from 7 to 90 nm.

If there is a single sublayer of type Si ₃ N ₄ , the thickness is, for example, 5 to 30 nm, specifically about 10 to 15 or 20 nm. If the sublayer is an arrangement of several layers, each layer can have a thickness of, for example, 5 to 50 nm, in particular 15 to 45 nm.

The sublayer and / or coating layer may actually form part of the overlap of the dielectric layer. Therefore, the sublayer or covering layer can be merged with other layers having different refractive indices. Therefore, the multilayer stack may comprise three layers alternated between a plate and a functional layer (or on a functional layer) with a high refractive index / low refractive index / high refractive index layer, a “high refractive index” (at least 1.8 to 2) layer or the One of the layers may be an accessory layer of the invention of the Si ₃ N ₄ or AlN type and the “low refractive index” (eg less than 1.7) layer may be made of silicon oxide (SiO ₂ ).

The thickness of the further metal nitride layer is preferably 2 to 20 nm, specifically 5 to 10 nm. Therefore, the additional metal nitride layer is preferably thin, and therefore has a very small influence on the sunscreen effect added by the metal layer.

A preferred embodiment of the present invention is a stack comprising a functional layer based on niobium or niobium nitride, a coating layer based on silicon nitride and an optional sublayer based on silicon nitride.

값으로 특히 정량화될 수 있는 스택으로 이해된다.The subject matter of the present invention is also generally the above mentioned, plate material provided with bendable and / or toughenable and / or enamelable multilayer stacks. A “bendable and / or toughenable” stack is deposited on the plate within the meaning of the present invention, limited optically changed, and less than 3, in detail in the (L ^* , a ^* , b ^* ) colorimeter. Less than 2

It is understood as a stack that can be specifically quantified by value.

는 다음과 같이 정의된다.

, 여기서

,

및

는 열처리 전과 후의

,

및

측정치의 차이다.

Is defined as

, here

,

And

Before and after heat treatment

,

And

The difference between the measurements.

If the enamel composition is free of optical defects in the stack and exhibits limited optical changes and can be quantified as described above, the stack is considered "enamelable" if it can be deposited in the stack in a known manner. This also means that for a long time, once the stack has been baked or glazed, the stack has satisfactory durability without any unwanted degradation of the layer of the stack in contact with the enamel.

This type of stack is, of course, advantageous if plates made of colorless transparent glass or of clear or bulk-tinted glass are used. However, glass plates or plates not made of glass, in particular plates made of hard and transparent polymeric materials such as polycarbonate or polymethyl methacrylate (PMMA) replacing glass, or particular polyurethanes or polyethylene terephthalates, such as By using a plate made of a flexible polymer material it is possible to simply utilize satisfactory durability rather than bendable / toughable properties. The flexible material can be secured to a rigid plate by making it attachable by various means, in order to be functional, or by lamination operations.

The subject matter of the present invention is also "monolithic" glazing (ie glazing comprising a single plate) or double glazing type of insulating multiple glazings. Preferably, monolithic glazing or double glazing, the multilayer stack is on the second side (by convention, the glass / plate face of the glazing assembly is numbered internally outside of the compartment / room to which it is fitted). Are located and provide sun protection.

,

,

) 측색계에서 (어떠한 가능한 열처리 전후에) 음의 a^* 및 b^* 값을 갖는 청색 또는 녹색 칼라를 갖는 것이 바람직하다. 그리하여, 반사 시에 눈에 띠며 아주 강하지 않는 칼라가 바람직하게는 건축물에서 얻어진다.More particularly, advantageous glazings according to the invention have a T _L of about 5 to 55%, in particular 8 to 45% and less than 50%, in particular having a solar factor (SF) similar to the T _L value. This glazing is also particularly effective at the time of external reflection (on the side of the plate where no layer is provided)

,

,

It is preferred to have a blue or green color with negative a ^* and b ^* values (before and after any possible heat treatment) in the colorimeter. Thus, a color which is visible at reflection and not very strong is preferably obtained in the building.

The subject matter of the present invention is also a plate which has a multilayer stack and which is partly opaque by a coating of lacquer or enamel type to make curtain walls, wherein the opaque coating is in direct contact with the multilayer stack. The multilayer stack is therefore absolutely identical for window glazing and for curtain walling.

Applications specifically intended by the present invention are glazings for buildings, but other applications are also considered, particularly for windows of vehicles (except windshields that require very high transmission), such as side windows, sunroofs and rear windows. Can be.

The invention will be explained in more detail by way of non-limiting examples below.

All plates are made of 6 mm thick clear glass of the PLANIUX type sold by Saint-Gobain Vitrage.                 

All layers are deposited by a known method by magnetic field enhanced sputtering, where the metal layer uses a metal target in an inert atmosphere (100% Ar) and the metal nitride or silicon nitride layer is 100% relative to the active atmosphere containing nitrogen (TiN). 40% Ar / 60% N ₂ ) for N ₂ and Si ₃ N _{4 use an} appropriate metal or silicon {bulk doped with 8% aluminum} target. Therefore the Si ₃ N ₄ layer contains some aluminum.

Example 1

This example uses an Nb functional layer and a Si ₃ N ₄ overlayer according to the following arrangement.

Glass / Nb (30 nm) / Si ₃ N ₄ (31 nm).

After depositing the layer, the plate was heated by heating at 620 ° C. for 10 minutes.

Example 2

This example uses a functional layer and coating layer as in Example 1 according to the following arrangement, and a sublayer of Si ₃ N ₄ is added.

Glass / Si ₃ N ₄ (10 nm) / Nb (30 nm) / Si ₃ N ₄ (31 nm).

Thereafter, the coated plate was heat treated in the same manner as in Example 1.

Example 3

This example uses the same layer arrangement as Example 2 but with some variation in thickness.

Glass / Si ₃ N ₄ (10 nm) / Nb (33 nm) / Si ₃ N ₄ (27 nm).

After the layer was deposited, the plate was enameled on its side coated with a multilayer stack. The enamel composition was a standard of the type described in the patents mentioned above, for example FR-2 736 348, and the enamel treatment was carried out in a known manner with heat treatment at 620 ° C. to cure the enamel.

Example 4

This example repeats the layer arrangement in Examples 2 and 3, but with a thinner functional layer thickness for higher light transmittance of the glazing.

Glass / Si ₃ N ₄ (10 nm) / Nb (12 nm) / Si ₃ N ₄ (17 nm).

Thereafter, the coated plate was heat treated in the same manner as in Example 1.

Example 5

This example repeats the layer arrangement of Example 4 but a portion of the Nb functional layer thickness is “replaced” with a TiN layer added between the Nb functional layer and the coating layer.

The layer arrangement was as follows.

Glass / Si ₃ N ₄ (10 nm) / Nb (8 nm) / TiN (5 nm) / Si ₃ N ₄ (17 nm).

Thereafter, the coated plate was heat treated in the same manner as in Example 1.

Example 6

This example describes another embodiment of the present invention, wherein the functional layer is made of metal nitride, in this case niobium nitride.

The arrangement of the layers was as follows.

Glass / Si ₃ N ₄ (10 nm) / NbN (10 nm) / Si ₃ N ₄ (15 nm).

The Si ₃ N ₄ layer was obtained as before and the NbN layer was obtained using a niobium target in an active atmosphere containing 30% by volume nitrogen.

Comparative Example 1

This example is suitable for comparison with Example 1. Instead of the Nb functional layer, a functional layer made of a 40/60 NiCr alloy by weight ratio was used. The layer arrangement was as follows.

Glass / NiCr (30 nm) / Si ₃ N ₄ (27 nm).

The coated glass was then heat treated in the same manner as in Example 1.

Comparative Example 2

This example is suitable for comparison with Example 2. This uses a functional layer made of NiCr of 40/60 by weight instead of the Nb functional layer.

The layer arrangement was as follows.

Glass / Si ₃ N ₄ (10 nm) / NiCr (30 nm) / Si ₃ N ₄ (27 nm).

Thereafter, the coated plate was heat treated in the same manner as in Example 1.

Table 1 below combines the following characteristics for Example 1, Example 2 and Comparative Example 1 and Comparative Example 2.

° Transmittance:                 

: 광원 D₆₅ 하에서의 %단위의 광 투과율.Optical transmittance

: Light transmittance in% under light source D ₆₅ .

: 투과율에서 칼라의 ㎚단위의 주 파장(dominant wavelength).

: Dominant wavelength in nm of the color in the transmittance.

: 투과율에서 칼라의 %단위의 여기 순도(excitation purity).

: Excitation purity in% of color in transmittance.

° External reflectance (ie, measured externally when coated glass is fitted with monolithic glazing with a multilayer stack on the second side in the room):

).External reflectance in% (

).

(L, a ^* , b ^* ) A ^* _(REXT) , b ^* _(REXT) , which is the colorimetric coordinates of the external reflectance along the colorimetry system

° Internal reflectance: R _LINT value and colorimetric data in% a ^* _(RINT) , b ^* _(RINT)

° Energy transmittance: T _{E in} %.

, 외부 반사율에서의

및 내부 반사율에서의

이며, 여기서 투과율에 대해

이고, All these properties are given twice, once before heat treatment and once after heat treatment. Also measured is the transmittance

At external reflectance

And at internal reflectance

Where the permeability

ego,

이다.

to be.

This table shows that the T _L and T _E values of Examples 1 and 2 according to the invention are similar to provide a good T _L / T _E compromise before heat treatment. Ie Examples 1 and 2 provide good sun protection. Examples 1 and 2 are particularly good in terms of aesthetic appearance, as the a ^* and b ^* values are negative at external reflectance and their absolute values are not very high, up to 2.7. In other words, this value is not a very strong color but is blue-green, which is considered to be a favorite or glazing with strong external reflections.

값은 투과율, 내부 반사율 및 외부 반사율에 있어서 최대 2.7이고 외부 반사율에서

는 1.6밖에 안된다. 즉, 이것은 심각한 품질 저하 없이 굽힘 또는 강인화 타입의 처리가 될 수 있는 진정한 의미의 스택이다. 강인화되거나 어닐링되거나 굽혀질 수 있는 또는 그렇게 되지 않을 수 있는 유리를 갖는 것을 원하든 원치 않든 간에, 본 발명은 동일하게 유지되는 특성을 갖는 태양 차단 스택을 제공한다. 예 1에 관한 설명은 보다 더 적은 광학 변화를 갖는 예 2에도 적용된다. 즉, 특히, 외부 반사율에서

는 0.3밖에 안 된다.It is noteworthy that all these advantages are retained even after heat treatment. That is, the T _L and T _E values are kept within 1%, the change in colorimetric data is very small and does not change from one color to another in external reflection. There are no optical drawbacks.

Values are up to 2.7 for transmittance, internal reflectance and external reflectance and at external reflectance

Is only 1.6. In other words, this is a true stack that can be treated with bending or toughening type without significant quality degradation. Whether it is desired or not to have a glass that can be toughened, annealed, bent or not, the present invention provides a sun barrier stack having the same properties. The description of Example 1 also applies to Example 2 with fewer optical changes. That is, especially at the external reflectance

Is only 0.3.

The Si ₃ N ₄ Si ₃ N ₄ layer which is provided with at least greater than the thickness of the sub-layer with a thickness of 5 to 15 or 20㎚ can be seen that the glass. In other words, this results in a gain in toughening ability, while maintaining a satisfactory appearance upon reflection.

값은 본 발명에 의해 얻어진 값보다 적어도 3배 크며 기호 b^*는 외부 반사율에서 변한다. 즉, 칼라의 변화가 있다는 것이다. 이는 기능층에서 크롬을 가능한 한 제한하거나 없애는 것(예를 들어, 최대 20중량%, 상세하게는 최대 10중량% 또는 최대 5중량%)이 바람직하다는 사실을 확인시켜 주는데, 크롬은 고온에서 확산하는 특성 때문에 이러한 변화에서 아마도 어떤 역할을 할 것이다.The results for Comparative Examples 1 and 2 are significantly inferior. That is, this stack is not explicitly bendable / toughable within the meaning of the present invention. That is, the T _L and T _E values vary greatly. Therefore, in Comparative Example 1, T _L goes from 11.5% to almost 20%. Internal reflectance and external reflectance for Comparative Example 1

The value is at least three times larger than the value obtained by the present invention and the symbol b ^* varies in external reflectance. That is, there is a change in color. This confirms that it is desirable to limit or eliminate chromium as much as possible in the functional layer (for example up to 20% by weight, in particular up to 10% by weight or up to 5% by weight). Because of its nature, it may play a role in this change.

Table 2 below presents the parameters already described in Table 1 with respect to Example 3 in which enamel was deposited on the layer. That is, the values of R _LEXT , a ^* _(REXT) and b ^* _(REXT) were measured before and after enameling (the same fitting of the glazing as in Table 1, which is now curtain walling, ie layer and enamel on the second side) Monolithic glass).

Example 3 Enameled Transmittance External reflectance Internal reflectance T _L λd _(T) Pe _(T) R _LEXT a ^* _(REXT) b ^* _(REXT) ΔE R _LINT a ^* _(RINT) b ^* _(RINT) before after 7.7- 565- 2.4- 43.6 43.7 -3.2 -2.5 1.1 2.8 -1.0 35.5- 0.5- 18.4-

가 1로서 칼라가 대체로 동일하다는 것이 증명된다. 유리 상에 직접 동일한 에나멜이 증착되었기 때문에 커튼 월링의 노화(aging)는 표준 커튼 월링의 경우에서보다 현저하게 크지 않다.In the external reflectance after enameling,

As 1 it is proved that the colors are generally identical. The aging of the curtain walling is not significantly larger than in the case of standard curtain walling because the same enamel was deposited directly on the glass.

Table 3 below combines the parameters already described above for Examples 4-6 (monoglass with layers on the second side, in the same arrangement).                 

값 특히, 2보다 작은

값을 달성하는 것은 더욱 어렵다. 그러나 TiN층(예 6)을 부가함으로써, 2의 한계값보다 낮은

값을 만들 수 있다. 그러므로 TiN은 자체로서 측색적인 조절 역할과 특히 20%보다 큰 T_L을 갖는 다층 스택이 있는 글레이징의 외부 반사 시에 외관을 안정화시키는 역할을 한다.Therefore, the advantage of inserting additional TiN layers is described. That is, in this case the light transmittance is about 30%, whereas in the previous example the light transmittance was about 8%, for glazing with a multilayer stack having a relatively high light transmittance value, low

Value less than 2

It is more difficult to achieve a value. However, by adding a TiN layer (Example 6), it is lower than the limit value of 2

You can create a value. Therefore TiN itself acts as a colorimetric control and in particular stabilizes the appearance upon external reflection of the glazing with a multilayer stack having a T _L greater than 20%.

In particular, for the purpose of better adjusting the color of the glazing upon external reflection, examples 7 to 9 below were produced.

Example 7

This example uses a niobium nitride functional layer and two sublayers, i.e., a SiO ₂ layer (a refractive index of about 1.45) followed by a Si ₃ N ₄ layer (a refractive index of about 2).

The array was as follows:

Glass / Si ₃ N ₄ / SiO ₂ / NbN / Si ₃ N ₄ .

      (20 nm) (40 nm) (20 nm)

The thickness of the NbN layer was adjusted to obtain a light transmittance of 32%.

Example 8

This example is similar to Example 7, but the NbN layer is replaced with an Nb metal layer (thickness of 32% light transmittance again).

Therefore, the arrangement

It was glass / Si ₃ N ₄ / SiO ₂ / Nb / Si ₃ N ₄ .

      (20 nm) (40 nm) (20 nm)

Example 9

This example is similar to Example 8 but uses a triple sublayer, ie a high-index layer, a low-index layer and again a high index layer.

The array was as follows:

Glass / Si ₃ N ₄ / SiO ₂ / Si ₃ N ₄ / Nb / Si ₃ N ₄ .

      (30 nm) (30 nm) (20 nm) (30 nm) (27 nm)

The thickness of the Nb layer was adjusted to have a T _L of about 8%.

Table 4 below shows the same photometric properties for Examples 7 and 8 at the transmittance and external reflectance as already given in Table 1.

Yes Heat treatment Transmittance External reflectance T _L (%) λd (nm) Pe (%) ΔE _(T) R _LEXT a ^* _REXT b ^* _REXT ΔE _(R) Example 7 before after 32.3 489 2.3 - 15.3 1.7 -10.3 - 31.8 484 4.3 1.7 15.7 1.7 -9.1 2.0 Example 8 before after 32.2 572 3.7 - 13.3 1.0 -15.0 - 30.7 563 2.1 2.4 15.4 0.9 -11.8 4.3

Example 10 below uses a tantalum functional layer.

Example 10

This example uses the following layer arrangement.

Glass / Si ₃ N ₄ / Ta / Si ₃ N ₄ .

     (10 nm) (7 nm) (20 nm)

Table 5 below presents the same information for this example as given in Table 4.

Yes Heat treatment Transmittance External reflectance T _L (%) λd (nm) Pe (%) ΔE _(T) R _LEXT a ^* _REXT b ^* _REXT ΔE _(R) Example 10 before after 32.6 480 3.4 - 19 -0.7 -3.9 - 32.9 482 3.0 1.2 18.5 -1.2 -3.7 0.9

Therefore, this stack containing tantalum shows that the optical change after the toughening treatment is limited, which is particularly similar to that obtained with the NbN layer. The same advantages are obtained this time using tantalum nitride.

It may be considered to use molybdenum as the functional layer, which may result in a more blue color upon external reflection.

In conclusion, the sun protection glazing according to the invention is very advantageous for fitting to buildings, but its application to automobiles and other vehicles is not excluded. That is, it can be used for side windows, rear windows and sunroofs, and may have an enameled coating. Due to the fixed multilayer stack, in particular due to the desired T _L and T _E values, without changing the stack, the manufacture of window glazings which are not intended to be heat treated or which have to be bent / toughened / annealed and lacquered or enameled It is possible to produce curtain walls that are in perfect colorimetric harmony with the window glazing that can be treated. Therefore, it is possible to standardize the manufacture of an interference layer on a large plate, which is very advantageous from an industrial point of view.

값이 2 또는 심지어는 1.8이하인 강인화 가능한 태양 조절 글레이징이 개발되는 결과를 가져왔는데, 이는 주목할 만한 것이다. The present invention is in the external reflectance

The result was the development of toughened sun-controlled glazings with values of 2 or even less than 1.8, which is noteworthy.

It is also possible to make an enamelled multilayer coated curtain walling rather than a lacquer treatment, which is very advantageous from an industrial point of view (enamel treatment takes place during the toughening process, while lacquer treatment requires additional manufacturing steps).

As mentioned above, the present invention relates to glazings with thin stacks acting on solar radiation, in particular glazings used for thermal insulation and / or sun protection, and opaque glazings to form part of wall covering panels. Used to make

Claims (28)

A stack of thin layers that act on solar radiation and have a light transmittance (T _L ) of 5% to 55% and a solar factor (SF) of greater than 0% and less than 50%. As a transparent substrate provided, The stack comprises at least one functional layer of metallic nature and is based on niobium, niobium nitride, The functional layer is covered with at least one overlayer based on aluminum nitride, aluminum oxynitride, silicon nitride or silicon oxynitride or based on a mixture of at least two of these compounds, The stack includes at least one sublayer made of a transparent dielectric material between the plate and the functional layer, Wherein the geometric thickness of the coating layer is thicker than the geometric thickness of the sublayer, Transparent plate with a thin stack that acts on solar radiation. A stack of thin layers that act on solar radiation and have a light transmittance (T _L ) of 8% to 45% and a solar factor (SF) of greater than 0% and less than 50%. As a transparent substrate provided, The stack comprises at least one functional layer of metallic nature and is based on niobium, niobium nitride, The functional layer is covered with at least one overlayer based on aluminum nitride, aluminum oxynitride, silicon nitride or silicon oxynitride or based on a mixture of at least two of these compounds, The stack includes at least one sublayer made of a transparent dielectric material between the plate and the functional layer, Wherein the geometric thickness of the coating layer is thicker than the geometric thickness of the sublayer, Transparent plate with a thin stack that acts on solar radiation. A stack of thin layers that act on solar radiation and have a light transmittance (T _L ) of 5% to 55% and a solar factor (SF) of greater than 0% and less than 50%. As a transparent substrate provided, The stack comprises at least one functional layer of metallic nature and is based on niobium, niobium nitride, The functional layer is covered with at least one overlayer based on aluminum nitride, aluminum oxynitride, silicon nitride or silicon oxynitride or based on a mixture of at least two of these compounds, The stack includes at least one sublayer made of a material selected from silicon nitride or aluminum nitride, silicon oxynitride or aluminum oxynitride, and silicon oxide, between the plate and the functional layer, Wherein the geometric thickness of the coating layer is thicker than the geometric thickness of the sublayer, Transparent plate with a thin stack that acts on solar radiation. A stack of thin layers that act on solar radiation and have a light transmittance (T _L ) of 8% to 45% and a solar factor (SF) of greater than 0% and less than 50%. As a transparent substrate provided, The stack comprises at least one functional layer of metallic nature and is based on niobium, niobium nitride, The functional layer is covered with at least one overlayer based on aluminum nitride, aluminum oxynitride, silicon nitride or silicon oxynitride or based on a mixture of at least two of these compounds, The stack includes at least one sublayer made of a material selected from silicon nitride or aluminum nitride, silicon oxynitride or aluminum oxynitride, and silicon oxide, between the plate and the functional layer, Wherein the geometric thickness of the coating layer is thicker than the geometric thickness of the sublayer, Transparent plate with a thin stack that acts on solar radiation. The method according to any one of claims 1 to 4, wherein the coating layer and the auxiliary layer Based on silicon nitride, Transparent plate with a thin stack that acts on solar radiation. The method according to any one of claims 1 to 4, wherein the coating layer Characterized in that at least 1.2 times thicker than the accessory layer, Transparent plate with a thin stack that acts on solar radiation. 5. The stack of claim 1, wherein the stack comprises: A plurality of sublayers is included between the plate and the functional layer, Transparent plate with a thin stack that acts on solar radiation. The thickness of any one of claims 1 to 4, wherein the thickness of the functional layer It is characterized in that 5 to 50nm, Transparent plate with a thin stack that acts on solar radiation. The thickness of any one of claims 1 to 4, wherein the coating layer 5 to 120nm, characterized in that Transparent plate with a thin stack that acts on solar radiation. The thickness of any one of claims 1 to 4, wherein the thickness of the additional metal nitride layer is 2 to 20nm, characterized in that Transparent plate with a thin stack that acts on solar radiation. The stack of claim 1, wherein the stack is Using a functional layer of niobium or tantalum, a coating layer of silicon nitride, an optional sublayer of silicon nitride, and a selective layer of titanium nitride or niobium nitride directly above or below the functional layer. doing, Transparent plate with a thin stack that acts on solar radiation. The stack of claim 1, wherein the stack is Characterized by using a functional layer made of niobium nitride, a coating layer made of silicon nitride, and an optional accessory layer made of silicon nitride, Transparent plate with a thin stack that acts on solar radiation. The plate according to any one of claims 1 to 4, wherein Can be bent / toughened or enameled, Transparent plate with a thin stack that acts on solar radiation. The plate according to any one of claims 1 to 4, wherein Characterized in that it is made of transparent or bulk-tinted glass, or a flexible or rigid transparent polymeric material, Transparent plate with a thin stack that acts on solar radiation. Insulating multiple glazing of the double glazing type of the monolithic glazing or double glazing type incorporating the plate material according to any one of claims 1 to 4, The multilayer stack provides a solar radiation shielding effect on the surface of the monolithic glazing or the thermally insulating multiple glazings of the double glazing type, Glazing. The method of claim 15, wherein the glazing, In the surface of the plate, when the external reflection is blue or green, having a negative a ^* and b ^* value, Glazing. The plate according to any one of claims 1 to 4, wherein Characterized in that at least partially opaque by coating in the form of lacquers or enamels, Transparent plate with a thin stack that acts on solar radiation. delete delete A curtain walling type wall cladding panel incorporating the opaque sheet material according to claim 17. delete The method according to any one of claims 1 to 4, wherein the coating layer And at least 1.5 to 1.8 times thicker than said sublayer. The method according to any one of claims 1 to 4, wherein the sublayer, It is characterized in that the high-index layer and the low-index layer (low-index), such as Si ₃ N ₄ / SiO ₂ or Si ₃ N ₄ / SiO ₂ / Si ₃ N ₄ are alternately Transparent plate with a thin stack that acts on solar radiation. The thickness of any one of claims 1 to 4, wherein the thickness of the functional layer It is characterized in that 8 to 40nm, Transparent plate with a thin stack that acts on solar radiation. The thickness of any one of claims 1 to 4, wherein the coating layer It is characterized by the 7 to 90nm, Transparent plate with a thin stack that acts on solar radiation. The thickness of any one of claims 1 to 4, wherein the thickness of the additional metal nitride layer is 5 to 10nm, characterized in that Transparent plate with a thin stack that acts on solar radiation. delete delete